Ultraviolet resist, patterning method and use of ultraviolet resist

Abstract

Relates to the technical field of photoresists, specifically to ultraviolet resists, patterning methods and uses of ultraviolet resists. The ultraviolet resist contains an organic solvent, a photosensitizer and zirconium oxide nanoclusters. The general formula of the zirconium oxide nanoclusters is Zr x O y (OH) z L m wherein 2 ≦ x ≦ 20, 2 ≦ y ≦ 40, 0 ≦ z ≦ 40, 4 ≦ m ≦ 40, and L is a carboxy group-containing organic ligand. The photosensitizer has the structural formula (1), and in formula (1), R 1 is represented by formula (2), * represents the bonding site, and R 2 and R 3 are each independently selected from -F, -Cl, -Br or -I each time they appear. By selecting the photosensitizer, the exposure dose can be significantly reduced and the speed of the photoresist can be increased. <Chemical formula 1> JPEG2025518845000020.jpg34170<Chemical formula 2> JPEG2025518845000021.jpg17170

Description

Technical Field

[0001] The present invention claims priority based on a Chinese patent application filed with the China National Patent Office on June 21, 2022, with an application number of 202210701897.5 and an invention title of "Ultraviolet Resist, Patterning Method and Use of Ultraviolet Resist", and a Chinese patent application filed with the China National Patent Office on June 21, 2022, with an application number of 202210701894.1 and an invention title of "Ultraviolet Resist and Patterning Method of Ultraviolet Resist", and incorporates all the contents of the above Chinese patent applications by reference into the present invention. The present invention relates to the technical field of photoresists, and specifically to ultraviolet resists, patterning methods and uses of ultraviolet resists.

Background Art

[0002] At present, all large-scale integrated circuits in the semiconductor industry are processed and manufactured by photolithography technology. The integration, yield and cost of integrated circuits are directly determined by the resolution and line width of photolithography processing technology. Photolithography processing technology refers to a micro-nano processing technology that transfers the pattern on the mask to the exposed substrate by changing the solubility of the photoresist under the exposure beam. A photoresist is a mixed material sensitive to light or radiation. Current ultraviolet resists are mainly composed of a film-forming resin, a photosensitizer, a solvent and other additives, and the film-forming resin is the main component of the photoresist.

[0003] Currently commercially available ultraviolet resists are mainly photosensitive materials using high molecular compounds as film-forming resins, and require a large exposure dose during use and have low sensitivity.

Summary of the Invention

Problems to be Solved by the Invention

[0004] Therefore, the present invention provides an ultraviolet resist, a patterning method and a use of the ultraviolet resist with a small exposure dose and high sensitivity.

Means for Solving the Problem

[0005] One aspect of the present invention provides an ultraviolet resist, which contains an organic solvent, a photosensitizer, and zirconium oxide nanoclusters. The general formula of the zirconium oxide nanoclusters is Zr x O y (OH) z L m where 2 ≦ x ≦ 20, 2 ≦ y ≦ 40, 0 ≦ z ≦ 40, 4 ≦ m ≦ 40, and L is a carboxy group-containing organic ligand. The photosensitizer has the structural formula (1), and in formula (1), R 1 is represented by formula (2), and * represents the binding site. <Chemical Formula 1> JPEG2025518845000002.jpg34170<Chemical Formula 2> JPEG2025518845000003.jpg17170

[0006] R 2 and R 3 are each independently selected from -F, -Cl, -Br, or -I each time they appear.

[0007] Optionally, in the above ultraviolet resist, R 2 and R 3 are both -Cl.

[0008] Optionally, in the above ultraviolet resist, the carboxy group-containing organic ligand contains at least one of an acrylic ligand, a methacrylic ligand, a 1-hydroxy-2-naphthoic acid ligand, and a salicylic acid ligand.

[0009] Optionally, in the above ultraviolet resist, the mass percentage of the zirconium oxide nanoclusters in the organic solvent is 0.5% to 15%, and the mass percentage of the photosensitizer is 0.001% to 1%.

[0010] Optionally, in the above ultraviolet resist, the organic solvent contains at least one of ethyl lactate, anisole, propylene glycol monomethyl ether acetate, methyl isobutyl ketone, and isopropyl alcohol.

[0011] Another aspect of the present invention further provides a method for patterning an ultraviolet resist, the patterning method including: forming an ultraviolet resist film by spin-coating the above ultraviolet resist on a substrate and then drying; and exposing the ultraviolet resist film to ultraviolet lithography through a mask, and then developing in a developer to form a lithography pattern.

[0012] Optionally, the developer contains at least one of toluene, xylene, 1,2-diacetoxypropane, propylene glycol monomethyl ether acetate, ethylene glycol monobutyl ether acetate, isopropyl alcohol, isobutyl alcohol, isoamyl alcohol, 4-methyl-2-pentanol, isopropoxyethanol, 1-methoxy-2-propanol, 1-propoxy-2-propanol, 1-butoxy-2-propanol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, ethylene glycol butyl ether, propylene glycol ethyl ether, 2-heptanone, and 2-butanone.

[0013] Optionally, in the above method for patterning an ultraviolet resist, the light source for ultraviolet lithography exposure is ultraviolet light with a wavelength of 365 nm, deep ultraviolet light with a wavelength of 254 nm, or extreme ultraviolet light with a wavelength of 13.5 nm. Further, the exposure dose is 7 mJ / cm² or more when the light source for ultraviolet lithography exposure is deep ultraviolet light with a wavelength of 254 nm, and 300 mJ / cm² or more when the light source for ultraviolet lithography exposure is ultraviolet light with a wavelength of 365 nm. -2 or more, and 300 mJ / cm² -2 or more when the light source for ultraviolet lithography exposure is ultraviolet light with a wavelength of 365 nm.

[0014] Optionally, the above ultraviolet resist can also be used as an electron beam photoresist.

[0015] One aspect of the present invention provides an ultraviolet resist, which contains an organic solvent, a photosensitizer, and zirconium oxide nanoclusters. The general formula of the zirconium oxide nanoclusters is Zr x O y (OH) z L m , where 2 ≦ x ≦ 20, 2 ≦ y ≦ 40, 0 ≦ z ≦ 40, 4 ≦ m ≦ 40, and L is a carboxy group-containing organic ligand. The photosensitizer has the structural formula (1), where R 1 is any one of formula (3), formula (4), and formula (5), * represents the bonding site, and R 2 and R 3 are each independently selected from -F, -Cl, -Br, or -I each time they appear. <Chemical formula 1> JPEG2025518845000004.jpg34170<Chemical formula 3> JPEG2025518845000005.jpg17170<Chemical formula 4> JPEG2025518845000006.jpg20170<Chemical formula 5> JPEG2025518845000007.jpg23170

[0016] Optionally, in the above ultraviolet resist, R 2 and R 3 are both -Cl.

[0017] Optionally, in the above ultraviolet resist, the carboxy group-containing organic ligand contains at least one of an acrylic ligand, a methacrylic ligand, a 1-hydroxy-2-naphthoic acid ligand, and a salicylic acid ligand.

[0018] Optionally, in the above ultraviolet resist, the mass percentage of the zirconium oxide nanoclusters in the organic solvent is 0.5% to 15%, and the mass percentage of the photosensitizer in the organic solvent is 0.001% to 1%.

[0019] Optionally, in the above ultraviolet resist, the organic solvent contains at least one of ethyl lactate, anisole, propylene glycol monomethyl ether acetate, methyl isobutyl ketone, and isopropyl alcohol.

[0020] Another aspect of the present invention further provides a method for patterning an ultraviolet resist. The patterning method includes the steps of spin-coating the above ultraviolet resist on a substrate and then drying it to form an ultraviolet resist film, and exposing the ultraviolet resist film by ultraviolet lithography using a mask and then developing it in a developer to form a lithography pattern.

[0021] Optionally, the developer contains at least one of toluene, xylene, 1,2-diacetoxypropane, propylene glycol monomethyl ether acetate, ethylene glycol monobutyl ether acetate, isopropyl alcohol, isobutyl alcohol, isoamyl alcohol, 4-methyl-2-pentanol, isopropoxyethanol, 1-methoxy-2-propanol, 1-propoxy-2-propanol, 1-butoxy-2-propanol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, ethylene glycol butyl ether, propylene glycol ethyl ether, 2-heptanone, and 2-butanone.

[0022] Optionally, in the above method for patterning an ultraviolet resist, the light source for ultraviolet lithography exposure is ultraviolet light with a wavelength of 365 nm, deep ultraviolet light with a wavelength of 254 nm, or extreme ultraviolet light with a wavelength of 13.5 nm. Further, the exposure dose is 12 mJ / cm² or more when the light source for ultraviolet lithography exposure is deep ultraviolet light with a wavelength of 254 nm, and 200 mJ / cm² or more when the light source for ultraviolet lithography exposure is ultraviolet light with a wavelength of 365 nm. -2 as above, and 200 mJ / cm² -2 or more when the light source for ultraviolet lithography exposure is ultraviolet light with a wavelength of 365 nm.

Advantages of the Invention

[0023] The ultraviolet resist of the present invention uses zirconium oxide nanoclusters as a film-forming resin. Its single scale is only 1 nm to 5 nm, which is much smaller than the size of polymer chains (generally larger than 20 nm). Therefore, compared with conventional polymer resin-based photoresists, the ultraviolet resist of the present invention can photolithograph patterns with smaller line widths. When the film-forming resin of zirconium oxide nanoclusters effectively matches with a photosensitizer, the sensitivity of the ultraviolet resist is greatly improved, the exposure dose is greatly reduced, and the photolithography efficiency is greatly improved. Furthermore, due to the presence of metal oxides, the photoresist has excellent mechanical properties and etching resistance, and there is almost no deformation or peeling in the exposed pattern during the subsequent development process, and the pattern fidelity is high.

Brief Description of the Drawings

[0024]

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Figure 13B

Best Mode for Carrying Out the Invention

[0025] Reference will be made in detail to embodiments of the present invention, and one or more examples thereof will be described below. Each example is not intended to limit the present invention, but is provided for the purpose of explanation. In fact, it will be apparent to those skilled in the art that various modifications and changes can be made to the present invention without departing from the scope or spirit of the present invention. For example, features described or depicted as part of one embodiment may be used in another embodiment to yield a further embodiment.

[0026] Accordingly, the present invention is intended to embrace such modifications and changes as fall within the scope of the appended claims and their equivalents. Other objects, features, and aspects of the present invention will be disclosed in the following detailed description or will become apparent from the following detailed description. Those skilled in the art should understand that this discussion is merely illustrative of exemplary embodiments and is not intended to limit broader aspects of the present invention.

[0027] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terms used in the specification of the present invention herein are for the purpose of describing particular embodiments only and are not intended to limit the present invention. The term "and / or" as used herein includes any and all combinations of one or more of the associated listed items. As used herein, the terms "comprises," "comprising," "has," "having," "contains," or other variations thereof are intended to cover a non-exclusive inclusion. For example, a composition, step, method, article, or apparatus that comprises the listed elements is not necessarily limited to those elements and may include other elements not expressly listed or inherent to such composition, step, method, article, or apparatus elements.

[0028] In this specification and the claims, all numbers used to indicate amounts of components, physicochemical properties, etc. should be understood to be adjusted by the term "about" in all cases, unless otherwise indicated in the operating examples or otherwise specified. Therefore, for example, unless otherwise specified, the numerical parameters listed in the above specification and the appended claims are all approximate values, and those skilled in the art can appropriately change those approximate values to obtain the desired properties using the teachings disclosed herein. Numerical ranges represented by endpoints include all numbers within that range, as well as any ranges within that range. For example, 1 to 5 includes 1, 1.1, 1.3, 1.5, 2, 2.75, 3, 3.80, 4, and 5, etc.

[0029] The "sensitivity" of a photoresist refers to the minimum energy of light or the minimum amount of charge (in the case of an electron beam resist) incident per unit area that causes the entire photoresist to react. In the present invention, the unit of sensitivity of an ultraviolet resist is mJ / cm² (the smaller the numerical value, the higher the sensitivity of the photoresist). The unit of sensitivity of an electron beam photoresist is μC / cm² (the smaller the numerical value, the higher the sensitivity of the photoresist). The sensitivity of a photoresist may be reflected by the minimum exposure dose, that is, exposure dose = light intensity × exposure time. -2 represented by (the smaller the numerical value, the higher the sensitivity of the photoresist). The unit of sensitivity of an electron beam photoresist is μC / cm² -2 represented by (the smaller the numerical value, the higher the sensitivity of the photoresist). The sensitivity of a photoresist may be reflected by the minimum exposure dose, that is, exposure dose = light intensity × exposure time.

[0030] One aspect of the present invention provides an ultraviolet resist, which contains an organic solvent, a photosensitizer, and zirconium oxide nanoclusters. The general formula of the zirconium oxide nanoclusters is Zr x O y (OH) z L m wherein 2 ≤ x ≤ 20, 2 ≤ y ≤ 40, 0 ≤ z ≤ 40, 4 ≤ m ≤ 40, and L is a carboxyl group-containing organic ligand. The photosensitizer has the structural formula (1), and in formula (1), R 1 is represented by formula (2), * represents the bonding site, R 2 and R 3Each time it appears, it is independently selected from -F, -Cl, -Br, or -I. <Chemical formula 1> JPEG2025518845000008.jpg34170<Chemical formula 2> JPEG2025518845000009.jpg17170

[0031] The photosensitizer in the ultraviolet resist has a high photoacid generation efficiency. Since the acid generated by photolysis can rapidly cause a chemical reaction of zirconium oxide nanoclusters, the ultraviolet resist has high sensitivity, reducing the exposure dose.

[0032] The ultraviolet resist of the present invention uses zirconium oxide nanoclusters as a film-forming resin. Its single scale is only 1 nm to 5 nm, much smaller than the size of polymer chains (generally larger than 20 nm). Therefore, compared with conventional polymer resin-based photoresists, the ultraviolet resist of the present invention can photolithograph patterns with a smaller line width. When the film-forming resin of zirconium oxide nanoclusters is effectively compatible with the photosensitizer, the sensitivity of the ultraviolet resist is greatly improved, the exposure dose is greatly reduced, and the photolithography efficiency is greatly improved. Furthermore, due to the presence of metal oxides, the photoresist has excellent mechanical properties and etching resistance, and there is almost no deformation or peeling in the exposed pattern during the subsequent development process, and the pattern fidelity is high.

[0033] In some embodiments, R 2 and R 3 are both -Cl.

[0034] In some embodiments, the carboxyl group-containing organic ligand includes, but is not limited to, acrylic ligand, methacrylic ligand, 1-hydroxy-2-naphthoic acid ligand, salicylic acid ligand, etc.

[0035] In some embodiments, the mass percentage of zirconium oxide nanoclusters in the organic solvent may be 0.5% to 15%, or may be 1%, 1.5%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 14.5%, etc.

[0036] In some embodiments, the mass percentage of the photosensitizer in the organic solvent may be 0.001% to 1%, or may be 0.002%, 0.003%, 0.005%, 0.006%, 0.008%, 0.01%, 0.02%, 0.05%, 0.08%, 0.1%, 0.12%, 0.15%, 0.3%, 0.5%, 0.8%, etc.

[0037] In some embodiments, by selecting a solvent having good solubility for the photosensitizer and zirconium oxide nanoclusters as the organic solvent, the photosensitizer and zirconium oxide nanoclusters can be better dissolved and uniformly dispersed in the organic solvent. After spin-coating the ultraviolet resist on the substrate and drying to form an ultraviolet resist film, it can be ensured that the photosensitizer and zirconium oxide nanoclusters are uniformly dispersed in the ultraviolet resist film. After lithography exposure, the exposed area of the ultraviolet resist becomes difficult to dissolve in the developer, but the unexposed area of the ultraviolet resist can be accurately and rapidly dissolved in the developer. Preferably, the organic solvent may be any one commonly used in this field, including but not limited to ethyl lactate, anisole, propylene glycol monomethyl ether acetate, methyl isobutyl ketone, and isopropyl alcohol.

[0038] Another aspect of the present invention further provides a patterning method for an ultraviolet resist, and the patterning method includes a step of spin-coating the above ultraviolet resist on a substrate and then drying to form an ultraviolet resist film, and a step of exposing the ultraviolet resist film by ultraviolet lithography using a mask and then developing in a developer to form a lithography pattern.

[0039] In some embodiments, the developer includes, but is not limited to, at least one of toluene, xylene, 1,2-diacetoxypropane, propylene glycol monomethyl ether acetate, ethylene glycol monobutyl ether acetate, isopropyl alcohol, isobutyl alcohol, isoamyl alcohol, 4-methyl-2-pentanol, isopropoxyethanol, 1-methoxy-2-propanol, 1-propoxy-2-propanol, 1-butoxy-2-propanol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, ethylene glycol butyl ether, propylene glycol ethyl ether, 2-heptanone, and 2-butanone.

[0040] In some embodiments, the light source for ultraviolet lithography exposure is deep ultraviolet light with a wavelength of 254 nm or ultraviolet light with a wavelength of 365 nm. When the light source for ultraviolet lithography exposure is deep ultraviolet light with a wavelength of 254 nm, the exposure dose is 7 mJ / cm -2 or more, and when the light source for ultraviolet lithography exposure is ultraviolet light with a wavelength of 365 nm, the exposure dose is 300 mJ / cm -2 or more.

[0041] In some embodiments, the above ultraviolet resist can also be used as an electron beam photoresist. When performing lithography exposure using an electron beam as the light source, the exposure dose can be low and may be 120 μC / cm -2 or less.

[0042] In some embodiments, as the substrate, any one of the substrate materials commonly used in this field, such as a silicon wafer, a quartz wafer, a glass wafer, etc., may be selected.

[0043] In some embodiments, when forming a lithography pattern, it is necessary to block light with a mask so as to form an ultraviolet lithography pattern having a preset shape.

[0044] Another aspect of the present invention further provides an ultraviolet resist, which contains an organic solvent, a photosensitizer, and zirconium oxide nanoclusters. The general formula of the zirconium oxide nanoclusters is Zr x O y (OH) z L m where 2 ≦ x ≦ 20, 2 ≦ y ≦ 40, 0 ≦ z ≦ 40, 4 ≦ m ≦ 40, and L is a carboxyl group-containing organic ligand. The photosensitizer has the structural formula (1), and in formula (1), R 1 is a furylvinyl or benzodioxolane substituted or unsubstituted with an alkyl group, and R 2 and R 3 are each independently selected from -F, -Cl, -Br, or -I each time they appear. <Chemical Formula 1> JPEG2025518845000010.jpg34170

[0045] Since the ultraviolet resist of the present invention uses zirconium oxide nanoclusters as a film-forming resin, its single scale is only 1 nm to 5 nm, which is much smaller than the size of the polymer chain (generally larger than 20 nm). Therefore, compared with the conventional polymer resin type photoresist, the ultraviolet resist of the present invention can photoetch a pattern with a smaller line width. When the film-forming resin of zirconium oxide nanoclusters effectively matches with the photosensitizer, the sensitivity of the ultraviolet resist is greatly improved, the exposure dose is greatly reduced, and the photolithography efficiency is greatly improved. Furthermore, due to the presence of the metal oxide, the photoresist has excellent mechanical properties and etching resistance, and there is almost no deformation or peeling in the exposed pattern in the subsequent development process, and the pattern fidelity is high.

[0046] In some embodiments, R 1 is any one selected from the groups of the following formula (3), formula (4), and formula (5). In the formula, * represents the bonding site. <Chemical Formula 3> JPEG2025518845000011.jpg17170<Chemical Formula 4> JPEG2025518845000012.jpg20170<Hua 5> JPEG2025518845000013.jpg23170

[0047] In some embodiments, R 2 and R 3 are both -Cl.

[0048] In some embodiments, the photosensitizer is one or more of 2-(1,3-benzodioxolan-5-yl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-[2-(furan-2-yl)vinyl]-4,6-bis(trichloromethyl)-1,3,5-triazine, and 2-[2-(5-methylfuran-2-yl)vinyl]-4,6-bis(trichloromethyl)-1,3,5-triazine.

[0049] In some embodiments, the carboxy group-containing organic ligand includes, but is not limited to, acrylic ligands, methacrylic ligands, 1-hydroxy-2-naphthoic acid ligands, and salicylic acid ligands.

[0050] In some embodiments, the mass percentage of zirconium oxide nanoclusters in the organic solvent may be 0.5% - 15%, or may be 1%, 1.5%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 14.5%, etc.

[0051] In some embodiments, the mass percentage of the photosensitizer in the organic solvent may be 0.001% - 1%, or may be 0.002%, 0.003%, 0.005%, 0.006%, 0.008%, 0.01%, 0.02%, 0.05%, 0.08%, 0.1%, 0.12%, 0.15%, 0.3%, 0.5%, 0.8%, etc.

[0052] In some embodiments, by selecting a solvent having good solubility for the photosensitizer and zirconium oxide nanoclusters as the organic solvent, the photosensitizer and zirconium oxide nanoclusters can be better dissolved and uniformly dispersed in the organic solvent. After spin-coating the ultraviolet resist on the substrate and drying it to form an ultraviolet resist film, it can be ensured that the photosensitizer and zirconium oxide nanoclusters are uniformly dispersed in the ultraviolet resist film. After lithography exposure, the exposed area of the ultraviolet resist becomes less soluble in the developer, but the unexposed area of the ultraviolet resist can be accurately and rapidly dissolved in the developer. Preferably, the organic solvent may be any one or more commonly used in this field, including but not limited to ethyl lactate, anisole, propylene glycol monomethyl ether acetate, methyl isobutyl ketone, isopropyl alcohol, etc.

[0053] Another aspect of the present invention further provides a patterning method for an ultraviolet resist. The patterning method includes a step of spin-coating the above-mentioned ultraviolet resist on a substrate and then drying it to form an ultraviolet resist film, and a step of exposing the ultraviolet resist film by ultraviolet lithography using a mask and then developing it in a developer to form a lithography pattern.

[0054] In some examples, the developer includes at least one of toluene, xylene, 1,2-diacetoxypropane, propylene glycol monomethyl ether acetate, ethylene glycol monobutyl ether acetate, isopropyl alcohol, isobutyl alcohol, isoamyl alcohol, 4-methyl-2-pentanol, isopropoxyethanol, 1-methoxy-2-propanol, 1-propoxy-2-propanol, 1-butoxy-2-propanol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, ethylene glycol butyl ether, propylene glycol ethyl ether, 2-heptanone, and 2-butanone, but is not limited thereto.

[0055] In some embodiments, the light source for ultraviolet lithography exposure is deep ultraviolet light with a wavelength of 254 nm or ultraviolet light with a wavelength of 365 nm. The exposure dose is 12 mJ / cm -2 or more when the light source for ultraviolet lithography exposure is deep ultraviolet light with a wavelength of 254 nm, and may be 200 mJ / cm -2 or more when the light source for ultraviolet lithography exposure is ultraviolet light with a wavelength of 365 nm.

[0056] In some embodiments, as the substrate, any one of the substrate materials commonly used in this field may be selected, for example, a silicon wafer, a quartz wafer, a glass wafer, etc.

[0057] In some embodiments, when forming a lithography pattern, it is necessary to block light with a mask so as to form an ultraviolet lithography pattern having a preset shape.

[0058] Hereinafter, the ultraviolet resist, the patterning method and the use of the ultraviolet resist of the present invention will be described in more detail in accordance with specific examples. (Example 1)

[0059] 0.03 g of 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-S-triazine and 0.75 g of zirconium oxide nanocluster (Zr6O4(OH)4(CH2=CCH3COO) 12 ) were dissolved in 14.25 g of propylene glycol monomethyl ether acetate solvent and stirred until completely dissolved. Then, the ultraviolet resist solution was filtered twice with a filter membrane having a pore size of 0.22 μm. The filtered ultraviolet resist solution was put into a brown glass bottle and stored in the dark at room temperature.

[0060] An appropriate amount of the prepared ultraviolet resist solution was dropped onto the surface of a clean silicon wafer, and the rotation speed was 2000 rpm and the acceleration was 500 rpm / s -1The substrate material was placed in a spin coater and spin-coated for 1 minute. Then, the substrate material was taken out and placed in an adhesive dryer and dried at 90°C for 1 minute. Further, the substrate material was placed in an ultraviolet contact lithography apparatus, a mask was placed, and lithography exposure was performed using ultraviolet light with wavelengths of 254 nm and 365 nm as light sources. When performing lithography exposure using ultraviolet light with wavelengths of 254 nm and 365 nm as light sources, the exposure dose was 7 mJ / cm -2 and 300 mJ / cm -2 , and the development time was 15 seconds for both. After ultraviolet exposure, the substrate material was taken out, developed in 1,2-diacetoxypropane, and the developer remaining on the surface of the substrate material after development was dried with a nitrogen gas gun. The patterns obtained by lithography exposure with light sources of wavelengths 254 nm and 365 nm were observed with a metalloscope. The results are shown in FIGS. 1A, 1B, 2A, and 2B. (Example 2)

[0061] 0.01 g of 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-S-triazine and 0.5 g of zirconium oxide nanocluster (Zr6O4(OH)4(CH2 = CCH3COO) 12 ) were dissolved in 9.5 g of propylene glycol monomethyl ether acetate solvent and stirred until completely dissolved. Then, the electron beam photoresist solution was filtered twice through a filter membrane with a pore size of 0.22 μm. After filtration, the electron beam photoresist solution was placed in a brown glass bottle and stored in the dark at room temperature.

[0062] An appropriate amount of the prepared electron beam photoresist solution was dropped onto the surface of a clean silicon wafer, and the substrate material was spin-coated for 1 minute in a spin coater with a rotation speed of 2000 rpm and an acceleration of 500 rpm / s -1 . Then, the substrate material was taken out and placed in an adhesive dryer and dried at 90°C for 1 minute. Further, the substrate material was placed in an electron beam lithography apparatus, and lithography exposure was performed using an electron beam as a light source. When performing lithography exposure using an electron beam as a light source, the exposure dose was 120 μC / cm -2, The development time was 25 seconds. After electron beam exposure, the substrate material was taken out, placed in 1,2-diacetoxypropane for development, and the developer remaining on the surface of the substrate material after development was dried with a nitrogen gas gun. The pattern obtained by lithography exposure with an electron beam was observed with a high-resolution scanning electron microscope. The results are shown in Figure 3. The resolution of the pattern obtained by this lithography exposure with an electron beam was 60 nm.

[0063] Thus, the ultraviolet resist according to Example 2 was used for electron beam lithography, and a clear exposure pattern was obtained. When lithography exposure was performed using an electron beam as a light source, the exposure dose was low, 120 μC / cm -2 It may be as follows. (Example 3)

[0064] 0.03 g of 2-(1,3-benzodioxolan-5-yl)-4,6-bis(trichloromethyl)-1,3,5-triazine and 0.75 g of zirconium oxide nanocluster (Zr6O4(OH)4(CH2 = CCH3COO) 12 ) were dissolved in 14.25 g of propylene glycol monomethyl ether acetate solvent and stirred until completely dissolved. Then, the ultraviolet resist solution was filtered twice through a filter membrane with a pore size of 0.22 μm. After filtration, the ultraviolet resist solution was put into a brown glass bottle and stored in the dark at room temperature.

[0065] An appropriate amount of the prepared ultraviolet resist solution was dropped onto the surface of a clean silicon wafer, and the substrate material was placed in a spin coater with a rotation speed of 2000 rpm and an acceleration of 500 rpm / s -1 and spin-coated for 1 minute. Then, the substrate material was taken out and placed in an adhesive dryer and dried at 90 °C for 1 minute. Further, the substrate material was placed in an ultraviolet contact lithography apparatus, a mask was placed, and lithography exposure was performed using ultraviolet light with wavelengths of 254 nm and 365 nm as light sources. When lithography exposure was performed using ultraviolet light with wavelengths of 254 nm and 365 nm as light sources, the exposure dose was 12 mJ / cm -2 and 200 mJ / cm -2The development time was 15 seconds for all. After ultraviolet exposure, the substrate material was taken out, developed in 1,2-diacetoxypropane, and the developer remaining on the surface of the substrate material after development was dried with a nitrogen gas gun. The patterns obtained by lithography exposure with light sources of wavelength 254 nm and wavelength 365 nm were observed with a metallurgical microscope. The results are shown in FIGS. 6A, 6B and FIGS. 7A, 7B. (Example 4)

[0066] 0.03 g of 2-[2-(furan-2-yl)vinyl]-4,6-bis(trichloromethyl)-1,3,5-triazine and 0.75 g of zirconium oxide nanocluster (Zr6O4(OH)4(CH2=CCH3COO) 12 ) were dissolved in 14.25 g of propylene glycol monomethyl ether acetate solvent and stirred until completely dissolved. Then, the ultraviolet resist solution was filtered twice through a filter membrane with a pore size of 0.22 μm. After filtration, the ultraviolet resist solution was put into a brown glass bottle and stored in the dark at room temperature.

[0067] An appropriate amount of the prepared ultraviolet resist solution was dropped onto the surface of a clean silicon wafer, and the substrate material was placed on a spin coater with a rotation speed of 2000 rpm and an acceleration of 500 rpms -1 and spin-coated for 1 minute. Then, the substrate material was taken out and placed in an adhesive dryer and dried at 90°C for 1 minute. Further, the substrate material was placed in an ultraviolet contact lithography apparatus, a mask was placed, and lithography exposure was performed using ultraviolet light with wavelengths of 254 nm and 365 nm as light sources. When lithography exposure was performed using ultraviolet light with wavelengths of 254 nm and 365 nm as light sources, the exposure dose was 54 mJ / cm -2 and 800 mJ / cm -2 respectively, and the development time was 15 seconds for all. After ultraviolet exposure, the substrate material was taken out, developed in 1,2-diacetoxypropane, and the developer remaining on the surface of the substrate material after development was dried with a nitrogen gas gun. The patterns obtained by lithography exposure with light sources of wavelength 254 nm and wavelength 365 nm were observed with a metallurgical microscope. The results are shown in FIGS. 8A, 8B and FIGS. 9A, 9B. (Example 5)

[0068] 0.03 g of 2-[2-(5-methylfuran-2-yl)vinyl]-4,6-bis(trichloromethyl)-1,3,5-triazine and 0.75 g of zirconium oxide nanocluster (Zr6O4(OH)4(CH2=CCH3COO) 12 ) were dissolved in 14.25 g of propylene glycol monomethyl ether acetate solvent and stirred until completely dissolved. Then, the ultraviolet resist solution was filtered twice through a filter membrane with a pore size of 0.22 μm. After filtration, the ultraviolet resist solution was placed in a brown glass bottle and stored in the dark at room temperature environment.

[0069] An appropriate amount of the prepared ultraviolet resist solution was dropped onto the surface of a clean silicon wafer, and the substrate material was placed in a spin coater with a rotation speed of 2000 rpm and an acceleration of 500 rpms -1 and spin-coated for 1 minute. Then, the substrate material was taken out and placed in an adhesive dryer and dried at 90°C for 1 minute. Further, the substrate material was placed in an ultraviolet contact lithography apparatus, a mask was placed, and lithography exposure was performed using ultraviolet light with wavelengths of 254 nm and 365 nm as the light source. When lithography exposure was performed using ultraviolet light with wavelengths of 254 nm and 365 nm as the light source, the exposure dose amounts were 72 mJ / cm -2 and 3600 mJ / cm -2 , respectively, and the development time was 15 seconds for both. After ultraviolet exposure, the substrate material was taken out, developed in 1,2-diacetoxypropane, and the developer remaining on the surface of the substrate material after development was dried with a nitrogen gas gun. The patterns obtained by lithography exposure with light sources of wavelengths 254 nm and 365 nm were observed with a metalloscope. The results are shown in FIGS. 10A, 10B, 11A, and 11B. (Comparative Example 1)

[0070] Comparative Example 1 is almost the same as the preparation method of Example 1, except that the photosensitizer is 2-(4-methoxystyrene)-4,6-bis(trichloromethyl)-1,3,5-triazine and the exposure dose is different. The specific steps are as follows. 0.03 g of 2-(4-methoxystyrene)-4,6-bis(trichloromethyl)-1,3,5-triazine and 0.75 g of zirconium oxide nanocluster (Zr6O4(OH)4(CH2=CCH3COO) 12 ) were dissolved in 14.25 g of propylene glycol monomethyl ether acetate solvent and stirred until completely dissolved. Then, the ultraviolet resist solution was filtered twice through a filter membrane with a pore size of 0.22 μm. After filtration, the ultraviolet resist solution was put into a brown glass bottle and stored in the dark at room temperature.

[0071] An appropriate amount of the prepared ultraviolet resist solution was dropped onto the surface of a clean silicon wafer, and the substrate material was placed in a spin coater with a rotation speed of 2000 rpm and an acceleration of 500 rpms -1 and spin-coated for 1 minute. Then, the substrate material was taken out and put into an adhesive dryer and dried at 90°C for 1 minute. Further, the substrate material was put into an ultraviolet contact lithography apparatus, a mask was placed, and lithography exposure was performed using ultraviolet light with wavelengths of 254 nm and 365 nm as the light source. When lithography exposure was performed using ultraviolet light with wavelengths of 254 nm and 365 nm as the light source, the exposure doses were 18 mJ / cm -2 and 400 mJ / cm -2 , respectively, and the development time was 15 seconds in both cases. After ultraviolet exposure, the substrate material was taken out, developed in 1,2-diacetoxypropane, and the developer remaining on the surface of the substrate material after development was dried with a nitrogen gas gun. The patterns obtained by lithography exposure with light sources having wavelengths of 254 nm and 365 nm were observed with a metal microscope. The results are shown in FIGS. 4A, 4B, 5A, and 5B.

[0072] From the above Example 1 and Comparative Example 1, the following was confirmed. Under the conditions of ultraviolet light with wavelengths of 254 nm and 365 nm, in Example 1, when 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-S-triazine was selected as a photosensitizer and reacted with zirconium oxide nanoclusters, the exposure dose was 7 mJ / cm -2 and 300 mJ / cm -2 respectively. On the other hand, in the comparative example, when 2-(4-methoxystyrene)-4,6-bis(trichloromethyl)-1,3,5-triazine was selected as a photosensitizer and reacted with zirconium oxide nanoclusters, the exposure dose was 18 mJ / cm -2 and 400 mJ / cm -2 respectively. Thereby, compared with Comparative Example 1, when 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-S-triazine of Example 1 was used as a photosensitizer and reacted with zirconium oxide nanoclusters, the photosensitive effect was more excellent, and the exposure dose decreased by 61% and 25% respectively. Example 1 can significantly reduce the ultraviolet exposure dose of the photoresist and increase the lithography speed. (Comparative Example 2)

[0073] 0.03 g of N-hydroxynaphthalimide triflate and 0.75 g of zirconium oxide nanoclusters (Zr6O4(OH)4(CH2=CCH3COO) 12 ) were dissolved in 14.25 g of propylene glycol monomethyl ether acetate solvent and stirred until completely dissolved. Then, the ultraviolet resist solution was filtered twice through a filter membrane with a pore size of 0.22 μm. After filtration, the ultraviolet resist solution was put into a brown glass bottle and stored in the dark at room temperature.

[0074] An appropriate amount of the prepared ultraviolet resist solution was dropped onto the surface of a clean silicon wafer, and the rotation speed was 2000 rpm and the acceleration was 500 rpm / s -1The substrate material was placed in a spin coater and spin-coated for 1 minute. Then, the substrate material was taken out and placed in an adhesive dryer and dried at 90 °C for 1 minute. Further, the substrate material was placed in an ultraviolet contact lithography apparatus, a mask was placed, and lithography exposure was performed using ultraviolet light with wavelengths of 254 nm and 365 nm as light sources. When performing lithography exposure using ultraviolet light with wavelengths of 254 nm and 365 nm as light sources, the exposure dose amounts were 144 mJ / cm -2 and 6000 mJ / cm -2 , and the development time was 15 seconds in both cases. After ultraviolet exposure, the substrate material was taken out, developed in 1,2-diacetoxypropane, and the developer remaining on the surface of the substrate material after development was dried with a nitrogen gas gun. The patterns obtained by lithography exposure with light sources having wavelengths of 254 nm and 365 nm were observed with a metallurgical microscope. The results are shown in FIGS. 12A, 12B, 13A, and 13B.

[0075] From the above Examples 3 to 5 and Comparative Example 2, the following was confirmed. Under the conditions of ultraviolet light with wavelengths of 254 nm and 365 nm as the exposure light source, in Examples 3 to 5, when 2-(1,3-benzodioxolan-5-yl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-[2-(furan-2-yl)vinyl]-4,6-bis(trichloromethyl)-1,3,5-triazine, and 2-[2-(5-methylfuran-2-yl)vinyl]-4,6-bis(trichloromethyl)-1,3,5-triazine were respectively selected as photosensitizers and reacted with zirconium oxide nanoclusters, the exposure dose amounts were 12 mJ / cm -2 and 200 mJ / cm -2 , 54 mJ / cm -2 and 800 mJ / cm -2 , 72 mJ / cm -2 and 3600 mJ / cm -2 respectively. On the other hand, in Comparative Example 2, when a photosensitizer other than the photosensitizer defined in the present invention was selected and reacted with zirconium oxide nanoclusters, the exposure dose amounts were 144 mJ / cm -2 and 6000 mJ / cm -2Thus, the ultraviolet resist according to the embodiments of the present invention can react zirconium oxide nanoclusters with a limited photosensitizer with each other during exposure, significantly reducing the ultraviolet exposure dose of the photoresist and increasing the lithography speed.

[0076] Each of the technical features of the above embodiments can be arbitrarily combined. For the sake of simplicity of description, not all possible combinations of the technical features of the above embodiments are described. However, as long as there is no contradiction in the combination of these technical features, it should be considered within the scope described in this specification.

[0077] The above embodiments merely show some embodiments of the present invention, and the description is more specific and detailed, but it should not be understood as limiting the scope of the claims. Those skilled in the art should note that without departing from the concept of the present invention, some modifications and improvements can be made, and these belong to the protection scope of the present invention. Therefore, the protection scope of the present invention patent should be determined by the appended claims.

Claims

1. An ultraviolet resist, comprising an organic solvent, a photosensitizer, and zirconium oxide nanoclusters, wherein the general formula of the zirconium oxide nanoclusters is Zr ｘ O ｙ (OH) ｚ L ｍ where 2 ≤ x ≤ 20, 2 ≤ y ≤ 40, 0 ≤ z ≤ 40, 4 ≤ m ≤ 40, and L is a carboxyl group-containing organic ligand, wherein the photosensitizer has Structural Formula (1), and in Formula (1), R １ is represented by Formula (2), * represents the bonding site, and R ２ and R ３ are each independently selected from -F, -Cl, -Br, or -I each time they appear, characterized ultraviolet resist. <Chemical Formula 1> <Chemical Formula 2>

2. wherein said R ２ and R ３ are both -Cl, characterized ultraviolet resist according to Claim 1.

3. wherein the carboxyl group-containing organic ligand contains at least one of an acrylic ligand, a methacrylic ligand, a 1-hydroxy-2-naphthoic acid ligand, and a salicylic acid ligand, characterized ultraviolet resist according to Claim 1 or Claim 2.

4. wherein the mass percentage of the photosensitizer is 0.001% to 1%, characterized ultraviolet resist according to Claim 1 or Claim 2.

5. wherein the mass percentage of the zirconium oxide nanoclusters in the organic solvent is 0.5% to 15%, characterized ultraviolet resist according to Claim 1 or Claim 2.

6. The organic solvent contains at least one of ethyl lactate, anisole, propylene glycol monomethyl ether acetate, methyl isobutyl ketone, and isopropyl alcohol, and the ultraviolet resist according to claim 1 or claim 2 is characterized thereby.

7. A method for patterning an ultraviolet resist, comprising: spin-coating the ultraviolet resist according to any one of claims 1 to 6 on a substrate and then drying to form an ultraviolet resist film; irradiating the ultraviolet resist film with ultraviolet lithography through a mask and then developing the film in a developer to form a lithography pattern. The method for patterning an ultraviolet resist is characterized by including the above steps.

8. The developer contains at least one of toluene, xylene, 1,2-diacetoxypropane, propylene glycol monomethyl ether acetate, ethylene glycol monobutyl ether acetate, isopropyl alcohol, isobutyl alcohol, isoamyl alcohol, 4-methyl-2-pentanol, isopropoxyethanol, 1-methoxy-2-propanol, 1-propoxy-2-propanol, 1-butoxy-2-propanol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, ethylene glycol butyl ether, propylene glycol ethyl ether, 2-heptanone, and 2-butanone, and the method for patterning an ultraviolet resist according to claim 7 is characterized thereby.

9. The light source for the ultraviolet lithography exposure is ultraviolet light with a wavelength of 365 nm, deep ultraviolet light with a wavelength of 254 nm, or extreme ultraviolet light with a wavelength of 13.5 nm, and the method for patterning an ultraviolet resist according to claim 7 is characterized thereby.

10. The exposure dose is 7 mJ / cm when the light source for the ultraviolet lithography exposure is deep ultraviolet light with a wavelength of 254 nm. －２The above, when the light source for ultraviolet lithography exposure is ultraviolet light with a wavelength of 365 nm, is 300 mJ / cm －２ The method for patterning an ultraviolet resist according to claim 7, characterized in that it is the above.

11. An electron beam photoresist, characterized in that the ultraviolet resist according to any one of claims 1 to 6 is used as the electron beam photoresist.

12. An ultraviolet resist, containing an organic solvent, a photosensitizer, and zirconium oxide nanoclusters, The general formula of the zirconium oxide nanoclusters is Zr ｘ O ｙ (OH) ｚ L ｍ wherein 2 ≤ x ≤ 20, 2 ≤ y ≤ 40, 0 ≤ z ≤ 40, 4 ≤ m ≤ 40, and L is a carboxy group-containing organic ligand, The photosensitizer has the structural formula (1), wherein R １ is any one of formula (3), formula (4), and formula (5), * represents the bonding site, and R ２ and R ３ are each independently selected from -F, -Cl, -Br, or -I each time they appear, characterized ultraviolet resist. <Chemical formula 1> <Chemical formula 3> <Chemical formula 4> <Chemical formula 5>

13. The R ２ and R ３ are both -Cl, the ultraviolet resist according to claim 12.

14. The carboxy group-containing organic ligand contains at least one of an acrylic ligand, a methacrylic ligand, a 1-hydroxy-2-naphthoic acid ligand, and a salicylic acid ligand, the ultraviolet resist according to claim 12 or claim 13.

15. The ultraviolet resist according to claim 12 or claim 13, characterized in that the mass percentage of the photosensitizer in the organic solvent is 0.001% to 1%.

16. The ultraviolet resist according to claim 12 or claim 13, characterized in that the mass percentage of the zirconium oxide nanocluster in the organic solvent is 0.5% to 15%.

17. The ultraviolet resist according to claim 12 or claim 13, characterized in that the organic solvent contains at least one of ethyl lactate, anisole, propylene glycol monomethyl ether acetate, methyl isobutyl ketone and isopropyl alcohol.

18. A method for patterning an ultraviolet resist, comprising: spin-coating the ultraviolet resist according to any one of claims 12 to 17 on a substrate and then drying to form an ultraviolet resist film; exposing the ultraviolet resist film by ultraviolet lithography using a mask, and then developing the film in a developer to form a lithography pattern.

19. The method for patterning an ultraviolet resist according to claim 18, characterized in that the developer contains at least one of toluene, xylene, 1,2-diacetoxypropane, propylene glycol monomethyl ether acetate, ethylene glycol monobutyl ether acetate, isopropyl alcohol, isobutyl alcohol, isoamyl alcohol, 4-methyl-2-pentanol, isopropoxyethanol, 1-methoxy-2-propanol, 1-propoxy-2-propanol, 1-butoxy-2-propanol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, ethylene glycol butyl ether, propylene glycol ethyl ether, 2-heptanone and 2-butanone.

20. The patterning method of the ultraviolet resist according to claim 18, wherein the light source for the ultraviolet lithography exposure is ultraviolet light with a wavelength of 365 nm, deep ultraviolet light with a wavelength of 254 nm, or extreme ultraviolet light with a wavelength of 13.5 nm.

21. The exposure dose is 12 mJ / cm －２ or more when the light source for the ultraviolet lithography exposure is deep ultraviolet light with a wavelength of 254 nm, and 200 mJ / cm －２ or more when the light source for the ultraviolet lithography exposure is ultraviolet light with a wavelength of 365 nm. The patterning method of the ultraviolet resist according to claim 18, characterized by the above.

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